US3338820A - High conversion level hydrogenation of residuum - Google Patents

High conversion level hydrogenation of residuum Download PDF

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Publication number
US3338820A
US3338820A US611496A US61149666A US3338820A US 3338820 A US3338820 A US 3338820A US 611496 A US611496 A US 611496A US 61149666 A US61149666 A US 61149666A US 3338820 A US3338820 A US 3338820A
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liquid
boiling
catalyst
bed
vapor
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US611496A
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English (en)
Inventor
Ronald H Wolk
Seymour B Alpert
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Hydrocarbon Research Inc
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Hydrocarbon Research Inc
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Priority to FR82009A priority Critical patent/FR1498026A/fr
Priority to DEH60883A priority patent/DE1279265B/de
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Priority to US611496A priority patent/US3338820A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/30—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles according to the "fluidised-bed" technique

Definitions

  • This invention relates to improvements in the method of converting residual oils to lower boiling materials. It specifically concerns itself with maintaining an operable system at higher degrees of conversion than have been possible heretofore.
  • the primary objective is to obtain as high a level of conversion of the residuum-s as is compatible with long on-stream times.
  • the ultimate goal is, of course, to convert all of the charge stock boiling above 975 F. to lower boiling material such as gasoline, kerosene, jet fuel, diesel oil and heavy gas oil with the complete elimination of low grade liquids such as heavy fuel oil.
  • One of the unique features of such a system is that operating conditions are controlled so as to eliminate any substantial carryover of catalyst from the reaction zone.
  • the most critical feature of this type of operation is that the reaction zone is maintained at substantially isothermal conditions. It is therefore possible to utilize a higher average temperature, and because of the avoidance of high local temperatures, the catalyst tends to remain cleaner for longer periods of time.
  • any coke that might be formed is passed through the bed without difliculties, and the total pressure drop across the bed does not change.
  • the objectives of our invention are thus to permit an extended on-stream period of hydrogenation reaction on residuum and to permit the increase of conversion level of such reaction whereby the maximum yield of valuable products can be produced.
  • a feed 10 of a residuum may be combined with a catalyst 12 and fed by line 14 with hydrogen from line 16 through a reactor generally designated 18.
  • the reactor may have a liquid distributor and catalyst support 20 so that the liquid and gas passing upwardly through the reactor 18 will tend to put the catalyst in random motion.
  • the catalyst particle size range is usually a narrow size range for uniform expansion under controlled liquid and gas flow conditions. While the overall range is usually between 3 and 270 mesh (Tyler), we contemplate a socalled once through operation using catalyst in the 270 mesh range with a liquid velocity in the order of 1-10 gallons per minute per square foot of horizontal reaction space. Alternatively, larger catalyst, usually in the 320 mesh size, can be used by adequate recycle of heavy oil to provide from about to 60 gallons total liquid per minute per square foot of horizontal reactor space. The lifting effect of the hydrogen is also a factor in the buoyancy of the catalyst.
  • the catalyst bed may be expanded to have a definite level or interface indicated at 22 in the liquid. It will be apparent that the settled level of the catalyst, as when the liquid rate drops below a sustaining value, will be considerably lower than level 22. Normally, bed expansion should be at least 10% and seldom over 300% of the static level, and the liquid rate will be in the range of 1 to 60 gallons per minute per square foot of horizontal cross section of the reactor.
  • a vapor space 23 from which a vapor overhead, completely free of liquid is removed at 24.
  • This may be conveniently cooled and partially condensed in heat exchanger 26 and separated in separator 28 into a gaseous portion removed overhead at 30, and a liquid portion removed at 32.
  • the gaseous portion 30, which is largely hydrogen, may be purified by conventional means 40 and after being reheated, can be recycled through compressor 42 to the feed line 14 to the reactor.
  • the liquid portion 32 from separator 28 is cooled in heat exchanger 34 and then fractionated in distillation column 36 into fractions boiling in the gasoline range (overhead), kerosene and diesel oil (side streams), and a heavy gas oil (bottoms).
  • a heavy liquid, free of catalyst, is separated from the liquid efliuent in the upper part of reactor 18 by trap tray 43, such liquid in line 44 passing through reducing valve 52 and being fractionated without cooling, in distillation column 60.
  • light products such as light gas
  • kerosene and diesel oil boiling range materials are removed as side streams 62 and 63.
  • a fuel oil fraction is removed at 64 as bottoms.
  • the hydrogenation reaction is facilitated by the use of catalyst 'and if a finely ground catalyst is used, it is effectively introduced to the reactor at 12 wherein it may be added continuously in the desired concentration as in a slurry. Catalyst may also be added to the reactor 18 through suitable inlet means 48 and withdrawn by suitable draw-off means 50.
  • Circulation of liquid from above the interface 22 to below the distributor deck 20 is usually desirable to assure completeness of thereaction and to establish a sufficient upflow liquid velocity to assist in maintaining the catalyst in random motion (ebullated) in the liquid.
  • This is preferably accomplished by the use of a central conduit 51 having an enlarged conical or funnel type cap 53.
  • the conduit extends to a pump 21 below the distributor deck 20 to assure a positive and controlled movement of the liquid downwardly.
  • Design and operation of the vapor section 23 of the reactor is critical to the successful operation of the entire plant. As above noted, vapors and gas bubbles must be removed. In addition, the vapor stream must be free of droplets or mist for the asphaltenic materials present in these liquid droplets will be completely precipitated by the high ratio of paraffinic naphtha that is present when all of the condensible materials in this stream are in the liquid form. This would, of course, result in fouling of all exchanger surfaces, pipe surfaces, valves and vessel walls.
  • Valve 54 on the heavy liquid drawotf line 44 is interconnected by control 55 to establish continuous, and uniform operating conditions once the liquid level is established. This is accomplished, for particular operating conditions, as by sampling or inspecting the overhead and maintaining at least a minimum liquid level 56 over the cap 53 on the recycle conduit 51.
  • Example I A bench scale reactor having a capacity of 1000 cc. was used to process West Texas sour vacuum residuum to a conversion of of the 975 F.+ material boiling in the feed to lighter product.
  • Example II In attempting to run Mid-Continent vacuum bottoms feed, it was found that an upper limit of 75% conversion was obtained at 2250 pounds per square inch gauge because of the deposition of sediment in the product line carrying the total reactor eflluent from reactor conditions to ambient temperatures. The bench scale unit was changed so that liquid and vapor streams could be removed separately from the reactor. It was then possible to operate at a conversion of 89.5% which is far superior in terms of the amounts of lighter products made from the feed. The overall product yields for the two cases are given in Table III:
  • the residuum is of a type containing at least 5% (wt) of asphaltenes, it' is normally of the type having at least 30% (vol.) of a fraction boiling above 975 F. In such case, we can continuously operate under conditions to convert in excess of 60% (vol.) of the residuum to materials boiling below 975 F. and frequently above 90% (vol.).
  • Such fraction usually contains 20 wt. percent or more of a fraction boiling in theC; to 600 F. range.
  • the useful range is about 1500 to 5000 p.s.i.g.
  • Temperatures will be in the range of 800 to 900 F. and, as before mentioned, liquid flow rates will be sufficient to expand the catalyst bed the desired amount. Liquid velocities will not normally exceed gallons per minute per square foot of horizontal cross section of the reactor. Space velocity is in the range of 0.2. to 2.0 vf./hr./vr., usually 0.4 to 1.5.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US611496A 1966-10-28 1966-11-29 High conversion level hydrogenation of residuum Expired - Lifetime US3338820A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
FR82009A FR1498026A (fr) 1966-10-28 1966-10-28 Procédé d'hydrogénation d'huiles de pétrole
DEH60883A DE1279265B (de) 1966-10-28 1966-10-28 Verfahren zur katalytischen Hydrocrackung von Erdoel
US611496A US3338820A (en) 1966-10-28 1966-11-29 High conversion level hydrogenation of residuum

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR82009A FR1498026A (fr) 1966-10-28 1966-10-28 Procédé d'hydrogénation d'huiles de pétrole
US611496A US3338820A (en) 1966-10-28 1966-11-29 High conversion level hydrogenation of residuum

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441498A (en) * 1967-03-15 1969-04-29 Atlantic Richfield Co Hydrogenation method and apparatus
US3477944A (en) * 1967-12-26 1969-11-11 Cities Service Res & Dev Co Maintenance of fluid flow in heavy hydrocarbon oil hydrogenation
US3544447A (en) * 1967-12-19 1970-12-01 Cities Service Res & Dev Co Heavy oil hydrocracking process
US3617524A (en) * 1969-06-25 1971-11-02 Standard Oil Co Ebullated bed hydrocracking
JPS4842684B1 (fr) * 1967-12-26 1973-12-14
US4172814A (en) * 1977-02-28 1979-10-30 The Dow Chemical Company Emulsion catalyst for hydrogenation processes
US4192735A (en) * 1976-07-02 1980-03-11 Exxon Research & Engineering Co. Hydrocracking of hydrocarbons
JPS58101192A (ja) * 1981-11-02 1983-06-16 ハイドロカ−ボン・リサ−チ・インコ−ポレ−テツド 石油供給原料の接触水素化転化方法
FR2528445A1 (fr) * 1982-06-15 1983-12-16 Chiyoda Chem Eng Construct Co Procede pour l'hydrocraquage d'huiles hydrocarbonees lourdes et catalyseur utilise a cet effet
US4476012A (en) * 1981-04-30 1984-10-09 Uop Inc. Process for deashing primary coal liquids
US5098552A (en) * 1988-06-27 1992-03-24 Texaco Inc. Controlling foam circulation in an ebullated bed process
WO2020192959A3 (fr) * 2019-03-28 2020-11-19 Gea Tds Gmbh Procédé et dispositif de contrôle de la production d'un extrait par extraction solide-liquide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3151060A (en) * 1961-11-22 1964-09-29 Hydrocarbon Research Inc Process and apparatus for liquid-gas reactions
US3215617A (en) * 1962-06-13 1965-11-02 Cities Service Res & Dev Co Hydrogenation cracking process in two stages

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3151060A (en) * 1961-11-22 1964-09-29 Hydrocarbon Research Inc Process and apparatus for liquid-gas reactions
US3215617A (en) * 1962-06-13 1965-11-02 Cities Service Res & Dev Co Hydrogenation cracking process in two stages

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441498A (en) * 1967-03-15 1969-04-29 Atlantic Richfield Co Hydrogenation method and apparatus
US3544447A (en) * 1967-12-19 1970-12-01 Cities Service Res & Dev Co Heavy oil hydrocracking process
US3477944A (en) * 1967-12-26 1969-11-11 Cities Service Res & Dev Co Maintenance of fluid flow in heavy hydrocarbon oil hydrogenation
JPS4842684B1 (fr) * 1967-12-26 1973-12-14
US3617524A (en) * 1969-06-25 1971-11-02 Standard Oil Co Ebullated bed hydrocracking
US4192735A (en) * 1976-07-02 1980-03-11 Exxon Research & Engineering Co. Hydrocracking of hydrocarbons
US4172814A (en) * 1977-02-28 1979-10-30 The Dow Chemical Company Emulsion catalyst for hydrogenation processes
US4476012A (en) * 1981-04-30 1984-10-09 Uop Inc. Process for deashing primary coal liquids
JPS58101192A (ja) * 1981-11-02 1983-06-16 ハイドロカ−ボン・リサ−チ・インコ−ポレ−テツド 石油供給原料の接触水素化転化方法
FR2528445A1 (fr) * 1982-06-15 1983-12-16 Chiyoda Chem Eng Construct Co Procede pour l'hydrocraquage d'huiles hydrocarbonees lourdes et catalyseur utilise a cet effet
US5098552A (en) * 1988-06-27 1992-03-24 Texaco Inc. Controlling foam circulation in an ebullated bed process
WO2020192959A3 (fr) * 2019-03-28 2020-11-19 Gea Tds Gmbh Procédé et dispositif de contrôle de la production d'un extrait par extraction solide-liquide
KR20210143859A (ko) * 2019-03-28 2021-11-29 게에아 테데에스 게엠베하 고체-액체 추출에 의해 추출물의 제조를 제어하는 방법 및 장치
US12397243B2 (en) 2019-03-28 2025-08-26 Gea Tds Gmbh Method and device for controlling the production of an extract using a solid-liquid extraction process

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Publication number Publication date
FR1498026A (fr) 1967-10-13

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